Lubricant compositions



United States Patent 3,182,023 LUBRICANT COMPOSITIONS John J. Plemich, Hammond, Ind, and Paul C. Vienna, Calumet City, llll., assignors to Standard Oil Company, Chicago, Ill., a corporation of Indiana No Drawing. Filed Aug. 8, 1962, Ser. No. 215,542 7 Claims. (Cl. 252--46.7)

and (C) from about 25 to about 200%, based on the Weight of said thiophosphoryl derivative, of an amine of the group consisting of I-(Z-hydroxyethyl)-2-heptadecenyl imidazoline, dehydroabietyl amine, dihydreabietyl amine, tetrahydroabietyl amine and mixtures of said abietyl amines.

Lubricant compositions containing the thiophosphoryl derivative (compound B of the lubricant compositions of this invention) are described and claimed in Fields US.

Patent No. 2,970,110. The subject matter of said patent,

to the extent pertinent to this invention, is incorporated herein by reference. In the preparation of lubricant compositions in accordance with the aforesaid patent, it has been found that the above described thiophosphoryl derivative has marginal solubility in lubricating oils. This marginal solubility is a disadvantage, for the resultant final oil blends are hazy in appearance, have marginal storage stability over widely varying temperature ranges, and are more costly to prepare.

It has been discovered that the addition of minor amounts of a'specific amine, hereinafter described, overcomes the solubility problem of the thiophosphoryl derivative in lubricating oils. Consequently, said derivative can now be used in larger and more effective quantities for improving extreme pressure properties of lubricating oils. Improved oil blends that are clear in appearance and storage stable can now be economically prepared.

The lubricating base oils (component A of the lubricant composition of this invention) are hydrocarbon oils, petroleum oils, synthetic hydrocarbon lubricating oils such as those obtained by the polymerization of hydrocarbons, and other synthetic lubricating oils such as alkylene oxide type oils, for example, the Ucon Oils, polycarboxylic acid ester-type oils such as esters of adipic acid, sebacic acid, azelaic acid, etc. and other synthetic lubricating oils.

The thiophosphoryl derivative (component B), which can be prepared in accordance with US. 2,970,110 or in any other known manner, is used in amounts of from about 0.05% to about 10% in the above described lubrieating base oils.

The specific amines that have been found effective for solubilizing the thiophosphoryl derivative (component B) are amines of the group consisting of 1-(2-hydroxyethyl)- 3,182,023 Patented May 4, 1965 Z-heptadecenyl imidazoline, dehydroabietyl amine, dihydroabietyl amine, tetrahydroabietyl amine and mixtures of said abietyl amines. The aforesaid imidazoline, having the structural formula N C17H33C/ ?Hg lTI-CH CHgCH OH is commercially available under the trade name Amine 0.5!

The abietyl amines are primary amines attached to an alicyclic structure. The general structural formulae of the above-named abietyl amines are:

( H O CH NH H CH Dehydroabietyl amine (H) H30 OH2NH2 l l H O CH ALE ta.

Dihydroabietyl amine (III) 11 0 CH NI I H CH 11 CIH3 Tetrahydroabietyl amine A particularly well suited amine is a product marketed by Hercules Powder Company as Rosin Amine D. This product is prepared by the catalytic hydrogenation of Rosin Nitrile D prepared by the action at elevated temperatures of ammonia on hydrogenated rosin. Distilled and undistilled grades are available as Amine 750 and Amine 751. The Rosin Amine D is a mixture of abietyl amines in the following approximate proportion:

Percent Dehydroabietyl amine 60 Dihydroabietyl amine 30 Tetrahydroabietyl amine 10 The amount of the amine (component C) used for solubilizing the thiophosphoryl derivative (component B) is from about 25 to about 200%, preferably from about 50 to about based on the weight of said thiophosphoryl derivative present in the lubricant composition.

The preparation of the lubricant compositions of this invention can be effected in any known manner. For example, component B can be added, with stirring, before or after or concurrently with component C to the base oil with or without the application of heat to the mixture. Preferably they are added as a premixed oil concentrate to the base oil at elevated temperatures.

Concentrates of a suitable oil base containing more than of the thiophosphoryl derivative in combination with a solubilizing amount of the appropriate amine can be formed by adding the base oil and the amine to the reaction medium used in preparing the thiophosphoryl derivative. Normally, the thiophosphoryl derivative is prepared in an inert solvent reaction medium such as toluene. Consequently, the addition of the base oil and the amine to the reaction medium to form the additive concentrate is best accomplished by addition just prior to removal of the inert solvent reaction medium. The resulting concentrate is a fluid and readily soluble in oil. Such concentrate, either alone or in combination with other lubricant additives, can be used-for blending with other oils in proportions desired for the particular condition or use to give a finished product containing from about 0.05% to about 10% of the thiophosphoryl derivative.

Compositions containing the thiophosphoryl derivative and amine combination can contain other addition agents, such as for example, antioxidants, pour point depressors, V.I. improvers, etc.

Unless otherwise stated, percentages given herein and in the appended claims are weight percentages.

The invention is illustrated in the following examples.

EXAMPLE 1 Lubricating oil compositions comprising a petroleum base oil (a 1:1 blend of unextracted SAE and 50 base oils), the thiophosphoryl derivative and amine additives were prepared. The oil-soluble amine additives used were Amine O (I-(Z-hydroxyethyl) 2 heptadecenyl imidazoline), Rosin Amine D (mixtures of abietyl amines), Primene 81-R, and Duomeen 0, all commercially available. The amine identified as Primene 8l-R is a mixture of C1248 tertiary alkyl primary amines having the formula wherein R, R and R" are straight or branched-chain alkyl radicals. Duomeen O is an N-alkyl trimethylene diamine having the formula whcelrein R represents an alkyl group derived from oleic aci The preparation of the lubricating oil compositions was accomplished by vigorously stirring the base oil, and the thiophosphoryl derivative with or without the amine additive at about 250 F. The presence of Rosin Amine D or Amine O effected complete solubilization in about onehalf hour; but continued heating and stirring of the other oil mixtures at 250 F. for about 2 hours failed to put the thiophosphoryl derivative into solution. The oil compositions containing the Rosin Amine D and Amine O additives were clear; whereas the other oils were hazy due to suspended small collodial particles of the thiophosphoryl derivative.

The solubility of the thiophosphoryl derivative in the oil was determined by appearance of the oil after blending the derivative with or without the amine additives; and after storage of the final oil blends at room temperature (68-75 F.) and at 40 F. The amount of thiophosphoryl derivative and amine used in preparing the oil blends and the apperance of the oils is set forth in the following table.

4 Table Thiophosphoryl Appearance of Oil at- Derivative, Amine Additive, Wt.

Wt. Percent Percent;

(SS-75 F. 40 F.

.0 0.5-Primene 81R 1.5-Primene 81-R. 1.0Rosin Amine l.5-Rosin Amine D. 1.0-Arnine O 1.0Duomeen O Ha7.y

The extreme pressure properties of lubricating oil containing the thiophosphoryl derivative alone and with Rosin Amine D were ascertained in accordance with the conevntional Timken and SAE extreme pressure methods. A solvent-extracted SAE 40 petroleum oil containing 3% of the thiophosphoryl derivative had a Timken value of 60 pounds and an SAE value of 350 pounds. The same base oil containing 3% of the thiophosphoryl derivative and 1.5% Rosin Amine D had a Timken value of 40 pounds and an SAE value of 385 pounds.

It is apparent that lubricant composition prepared in accordance with this invention have extreme pressure properties substantially equivalent to lubricant compositions containing the thiophosphoryl derivative but no amine additive.

Thus having described the invention, what is claimed 1. A lubricant composition (A) a major proportion of a lubricating oil, (B) from about 0.05 to about 10% of a thiophosphoryl derivative having the formula C1 H s 0 o1-o- J--(i -oH,0 ii-s-on-ii-MI o1, H -C-OH o1- O-H H and (C) from about 25 to about 200%, based on the weight of said thiophosphoryl derivative, of an amine of the group consisting of 1-(2-hydroxyethyl)-2-heptadecenyl imidazoline, dehydroabietyl amine, dihydroabietyl amine, tetrahydroabietyl amine and mixtures of said abietyl amines.

2. The composition of claim 1 wherein said oil is a petroleum lubricating oil.

3. The composition of claim 1 wherein said amine is 1(2-hydroxyethyl)-2-heptadeeenyl imidazoline.

4. The composition of claim 1 wherein said amine is a mixture of said abietyl amines.

5. The composition of claim 2 wherein the amount of said amine is from about 50 to about 6. An additive concentrate for lubricating oils comprising a lubricating oil containing (A) more than 10% of a thiophosphoryl derivative having the formula and (B) an amount, based on the weight of and sufficient to solubilize said thiophosphoryl derivative in said oil, of an amine of the group consisting of 1-(2-hydroxyethy1)-2-heptadecenyl imidazoline, dehydroabietyl amine, dihydroabietyl amine, tetrahydroabietyl amine and mixtures of said abietyl amines, said concentrate being capable of dilution with a lubricating oil to form a homogeneous lubricating oil containing from about 0.05 to about 10% of said thiophosphoryl derivative and from about 25 to about 200%, based on the weight of said thiophosphoryl derivative, of said amine.

7. A petroleum lubricating oil containing (A) from about 1 to about 3% of a thiophosphoryl derivative having the formula References Cited by the Examiner UNITED STATES PATENTS 2,970,110 1/61 Fields et a1. 252-46] FOREIGN PATENTS 551,067 12/57 Canada. 790,059 2/5 8 Great Britain. 796,408 6/ 5 8 Great Britain.

DANIEL E. WYMAN, Primary Examiner.

JAMES S. BAILEY, Examiner. 

1. A LUBRICANT COMPOSITION (A) A MAJOR PROPORTION OF A LUBRICATING OIL, (B) FROM ABOUT 0.05 TO ABOUT 10% OF A THIOPHOSPHORYL DERIVATIVE HAVING THE FORMULA 